Efficient Polyester Hydrogenolytic Deconstruction via Tandem Catalysis

Yosi Kratish*, Tobin J. Marks*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

35 Scopus citations


Using a mechanism-based solvent-free tandem catalytic approach, commodity polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are rapidly and selectively deconstructed by combining the two air- and moisture-stable catalysts, Hf(OTf)4 and Pd/C, under 1 atm H2, affording terephthalic acid (or naphthalene dicarboxylic acid for PEN) and ethane (or butane for PBT) in essentially quantitative yield. This process is effective for both laboratory grade and waste plastics, and comingled polypropylene remains unchanged. Combined experimental and DFT mechanistic analyses indicate that Hf(OTf)4 catalyzes a mildly exergonic retro-hydroalkoxylation reaction in which an alkoxy C−O bond is first cleaved, yielding a carboxylic acid and alkene, and this process is closely coupled to an exergonic olefin hydrogenation step, driving the overall reaction forward.

Original languageEnglish (US)
Article numbere202112576
JournalAngewandte Chemie - International Edition
Issue number9
StatePublished - Feb 21 2022


  • PET
  • chemical recycling
  • hydrogenolysis
  • polyester plastics
  • tandem catalysis

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis


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